WO2007071729A2 - A process for the recovery of a brown food-grade sugar product from a sugar beet solution - Google Patents

A process for the recovery of a brown food-grade sugar product from a sugar beet solution Download PDF

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Publication number
WO2007071729A2
WO2007071729A2 PCT/EP2006/070008 EP2006070008W WO2007071729A2 WO 2007071729 A2 WO2007071729 A2 WO 2007071729A2 EP 2006070008 W EP2006070008 W EP 2006070008W WO 2007071729 A2 WO2007071729 A2 WO 2007071729A2
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Prior art keywords
sugar
molasses
product
beet
electrodialysis
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PCT/EP2006/070008
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French (fr)
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WO2007071729A3 (en
Inventor
Melvin P Carter
John Preben Jensen
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Danisco Sugar A/S
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Publication date
Application filed by Danisco Sugar A/S filed Critical Danisco Sugar A/S
Priority to US12/158,724 priority Critical patent/US20080299287A1/en
Priority to JP2008546447A priority patent/JP2009520484A/en
Priority to CA002634371A priority patent/CA2634371A1/en
Priority to EP06848671A priority patent/EP1963540A2/en
Publication of WO2007071729A2 publication Critical patent/WO2007071729A2/en
Publication of WO2007071729A3 publication Critical patent/WO2007071729A3/en

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    • CCHEMISTRY; METALLURGY
    • C13SUGAR INDUSTRY
    • C13BPRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B35/00Extraction of sucrose from molasses
    • C13B35/02Extraction of sucrose from molasses by chemical means
    • C13B35/06Extraction of sucrose from molasses by chemical means using ion exchange
    • CCHEMISTRY; METALLURGY
    • C13SUGAR INDUSTRY
    • C13BPRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00Purification of sugar juices
    • C13B20/12Purification of sugar juices using adsorption agents, e.g. active carbon
    • C13B20/123Inorganic agents, e.g. active carbon
    • CCHEMISTRY; METALLURGY
    • C13SUGAR INDUSTRY
    • C13BPRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00Purification of sugar juices
    • C13B20/14Purification of sugar juices using ion-exchange materials
    • CCHEMISTRY; METALLURGY
    • C13SUGAR INDUSTRY
    • C13BPRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00Purification of sugar juices
    • C13B20/18Purification of sugar juices by electrical means
    • CCHEMISTRY; METALLURGY
    • C13SUGAR INDUSTRY
    • C13BPRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B35/00Extraction of sucrose from molasses
    • C13B35/08Extraction of sucrose from molasses by physical means, e.g. osmosis
    • CCHEMISTRY; METALLURGY
    • C13SUGAR INDUSTRY
    • C13BPRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B50/00Sugar products, e.g. powdered, lump or liquid sugar; Working-up of sugar
    • C13B50/006Molasses; Treatment of molasses
    • C13B50/008Drying

Definitions

  • the present invention relates to the field of sugar m anufacturing industry and flavouring industry. More particularly, the invention relates to a process for the recovery of a brown food-grade sugar product from sugar beet solutions, which can be obtained from various beet sugar process streams, such as thin juice, thick juice and molasses.
  • the invention also relates to novel food-grade beet sugar products derived from a sugar beet solution.
  • the products of the invention are suitable for substituting the corresponding cane sugar derived products.
  • the products according to the invention can be selected from brown sugar, electrodialyzed molasses, treacle, syrup and combinations thereof.
  • Especially the invention relates to the production of food-grade beet molasses.
  • the invention also relates to edible products com prising said novel food-grade beet sugar products. I n a further aspect the invention relates to the use of electrodialysis for removing m alodorous volatile components from a sugar beet solution.
  • Molasses is the final syrup residue remaining after crystallisation of sugar from either cane or beet juices. Only the syrup left from the final crystallisation stage is called molasses; intermediate syrups are referred to as high green and low green and these are recycled within the crystallisation process to m axim ise extraction. Molasses is one of the most valuable by-products of the sugar m anufacturing process. Both beet and cane molasses are widely used in the fermentation industries and in animal feed but only cane molasses as a food ingredient.
  • molasses that com es from the sugar beet is different from cane molasses.
  • Beet molasses contains over 50% sugar by dry weight, predom inantly sucrose but also containing sm all amounts of glucose and fructose.
  • the non-sugar content includes e.g. am ino acids, organic acids, and m any salts such as calcium , potassium , oxalate and chloride. These are either as a result of concentration from the original plant material or as a result of chem icals used in the processing.
  • beet molasses is generally known to be very unpalatable and is m ainly used as an additive to animal feed or as a fermentation feedstock.
  • syrups of cane origin are used (Sugar Technology Beet and Cane Sugar Manufacture, P. W. van der Poel, H Schiweck, T. Schwartz, 1998, p 967 section 19.6) .
  • Known substitutes in bakery product for syrups of cane origin are corn syrup, pure m aple syrup or even honey. However, these are more expensive than cane molasses.
  • One of the aspects of this invention is the production of palatable syrup of beet origin suitable as an ingredient in brown sugars and brown syrups. This is done with the aid of electrodialysis.
  • pyrazines found in beet molasses do not exist in cane molasses and are one of the compounds distinguishing these two products.
  • Pyrazines are form ed in alkaline conditions in the presence of glucose and am ino acids, which have great chem ical reactivity with respect to carbonyl com pounds, through the Maillard reaction.
  • Beet juices contain m uch higher levels of am ino acids than cane juice (Sugar Technology Beet and Cane Sugar Manufacture, P.W. van der Poel, H Schiweck, T. Schwartz, 1998, p 143 and 156) in which m any of the am ino acids are only present in trace amounts.
  • the higher levels of am ino acids in beet juices and the higher operating pH in the conventional beet sugar process are two factors which can explain the presence of pyrazines in sugar beet juices like thin juice, thick juice and molasses.
  • Pyrazines are known to be powerful arom a com pounds with odours ranging from nutty, roasted, m usty, to burnt solvent.
  • I dentification and quantification by Marsili et al (Journal of Chromatographic Science, 1994, 32, 165- 171 ) of com pounds responsible for the off-odour of beet sugar identified 2,5-dim ethyl pyrazine as one of the com pounds likely to contribute to the characteristic off-odour of beet sugar.
  • Marsili found also geosm in, acetic, butyric and isovaleric acids to produce odour characteristics of beet. Carbon treatm ent reduced acetic acid and also acetol levels. Acetol has a good odour, but is pungent in larger quantities.
  • Electrodialysis as a technique is known from the 1950's and it is widely used for exam ple in desalting of water and whey and within the inorganic chem ical industry e.g. for recovering organic acids from solutions. Desalting of sugar cane or sugar beet solutions via ED has been established in 1960's to 80's in various patent publications. Electrodialysis separates salts from a sugar solution using alternate cation and anion exchange m em branes. This is done by passing a direct current through a m embrane stack, causing the anions to move through the anion exchange mem brane and the cations through the cation exchange m embrane.
  • US 3 799 806 discloses a process for the purification and clarification of sugar juices, involving ultrafiltration followed by purification with electrodialysis. Sugar is separated by crystallisation from the purified juice.
  • US 3 781 174 discloses a continuous process for producing refined sugar from juice extracted from sugarcane. This process comprises further removing the impurities and colouring m atter by using a com bination of ion-exchange resin and ion-exchange m embrane electrodialysis, concentrating the purified juice and crystallizing the concentrated juice to form refined sugar.
  • US 4 331 483 discloses a process for purifying beet juice by contacting the juice to be purified with at least two ion exchangers formed of a porous m ineral support covered with a film of cross-linked polymer containing or bearing quaternary am monium salt groups for at least one of the ion exchangers and sulfone groups for at least one of the other ion exchangers.
  • the ion exchange is used for removing proteins, am ino acids and betaine.
  • the purified juice m ight be dem ineralized by ion exchange or electrodialysis. Sugar is then separated by crystallisation from the purified juice.
  • US 4 083 732 discloses a m ethod of treating fresh sugar cane juice at about room temperature which includes removing non-sugar impurities , concentrating the resulting cold, water white juice by reverse osmosis to form a syrup which is evaporated to form direct white sugar and edible molasses. Also a m ethod of removing ions from the syrup by electrodialysis to produce cane based edible molasses having a very low ash and m aple flavour is disclosed.
  • WO2003/018848 describes a process for the preparation of white and brown sugar from raw diffuser beet juice.
  • the juice is purified by m embrane filtration at 70 to 95 0 C on a filter having a cut-off between 2,000 and 500,000 Dalton and evaporated under vacuum to a thick juice.
  • concentration to dry m atter content of 25% to 35% by weight the m embrane filtrated juice can optionally be dem ineralized by electrodialysis and then further evaporated to a thick juice.
  • a conventional multi-step evaporative crystallisation of the thick juice gives crops of white and brown sugar crystals.
  • the brown sugar obtained has valuable organoleptic properties and produced molasses has a better taste and aroma than conventional beet molasses.
  • electrodialysis is known as a method for desalinating sugar cane syrup or molasses of a relatively high concentration.
  • sugar syrup or molasses it has been considered defective in that organic non-sugar contents would adhere to and precipitate on the anion exchange film and make cleaning of films difficult.
  • a m ethod for the reduction of fouling by the precipitation of calcium and silicon before electrodialysis is disclosed in US 4 492 601 .
  • I t describes a process for clarifying and desalinating sugar cane syrup or molasses, wherein inorganic oxy-acid and organic acid im purities are removed from raw sugar cane or molasses solutions by the steps of ( 1 ) adm ixing with the raw sugar cane syrup or molasses solution a water-soluble chloride of an alkaline earth m etal ion which reacts with inorganic oxy-acid anions and radicals and with organic acids to form a water-insoluble precipitate of said oxy-acid anions and radicals and organic acids, (2) separating said precipitate from said solution, (3) diluting the precipitate-free solution, and (4) subjecting said diluted solution to an electrodialysis using cation exchange film and neutral film arranged in an alternating m anner.
  • ion exchange technology does not provide an identical result to ED and that the regeneration of ion exchange resins necessarily involves the use of strong acids and bases while the ED resins are easily cleaned occasionally by an acid wash followed by an alkali wash with less chem icals than in ion exchange.
  • alkali m etal cations have been suspected of being highly melassigenic by holding sugar in the molasses and preventing it from being recovered as crystalline sugar.
  • Elm idaoui et al. (Elsevier, Desalination 148, 2002, pp. 143- 148) describe the removal of melassigenic ions especially Na + , K + and Ca 2+ for beet sugar syrups by electrodialysis using an anion-exchange membrane.
  • the objective problem to be solved is to provide brown food-grade sugar products having improved colour, taste, odour and/or arom a from a sugar beet solution.
  • An object of the present invention is thus to provide a process and a product so as to so as to alleviate the above disadvantages.
  • the objects of the invention are achieved by a process, product and uses which are characterized by what is stated in the independent claims.
  • the preferred embodim ents of the invention are disclosed in the dependent claims.
  • the invention is based on the surprising finding that electrodialysis (ED) can be used for removing m alodorous volatile components from a sugar beet solution. Especially, it was surprising that the undesired off-flavours and odours com prising pyrazines can be removed by ED. I t was known from the prior art to use ED for removal of ionic com pounds, but man skilled in the art would not have thought that non-ionic com pounds such as pyrazines could be removed as well.
  • An objective of the invention is to provide a process of treating sugar beet juices and especially norm al beet molasses to allow com suddenlyal food-grade brown sugar and molasses or blends thereof to be made suitable for use in both baking and confectionery.
  • electrodialysis removes undesired off- flavours and odours found in norm al beet molasses from conventional sugar beet process. I n this way a treated molasses can be produced suitable for direct production of food grade molasses absent of the off-odours normally associated with beet molasses.
  • a further advantage of the process is that the ED treatm ent increases the molasses purity by removing salts, which allows extra sugar to be crystallised from the molasses. Crystallisation followed by centrifugation and drying of the recovered crystalline sugar allows production of brown sugar absent of the off-odours normally associated with brown sugar from sugar beet origin.
  • Figure 1 is a schematic flow sheet of the inventive process according to an em bodim ent.
  • Figure 2 is a schematic flow sheet of the inventive process according to another em bodim ent.
  • “Sugar beet” (Beta vulgaris) , a m em ber of the Chenopodiaceae subfam ily and the Am aranthaceae fam ily, is a plant whose root contains a high concentration of sucrose.
  • "Beet sugar” is sucrose obtained from sugar beet and respectively "beet molasses” is molasses obtained from sugar beet.
  • a typical beet sugar production process com prises several steps. After reception at the processing plant the beet roots are washed, m echanically sliced, and passed to a diffuser to extract their sugar content into a water solution. The liquid, a sugar beet solution, exiting the diffuser is called "raw juice”.
  • the raw juice contains many impurities that m ust be removed before crystallisation. These purifications processes do not only purify raw juice but also alter the chem ical composition of the raw juice. As an example of the changes in the chem ical com position is the formation of malodorous volatiles in the sugar beet solution. Although some of the m alodorous volatiles probably enter the sugar factory with the beets, others such as organic acids and pyrazines are form ed during processing. For exam ple pyrazines (known malodorous compounds) are form ed by the reaction of glucose with am ino acids such as glutam ine and lysine in purification by carbonation process.
  • a typical purification process in a sugar factory is "carbonation" , wherein the juice is first m ixed with hot m ilk of lime (a suspension of calcium hydroxide in water) .
  • This treatment precipitates in some extent a num ber of im purities, including multivalent anions such as sulfate, phosphate, citrate and oxalate, which precipitate as their calcium salts and large organic molecules such as proteins, saponins and pectins, which aggregate in the presence of m ultivalent cations.
  • the alkaline conditions convert the sim ple sugars, glucose and fructose, along with the am ino acid glutam ine, to chem ically stable carboxylic acids and induce Maillard reaction and creation of unfavourable com pounds like pyrazines. Left untreated, these sugars and am ines would eventually frustrate crystallisation of the sucrose.
  • carbon dioxide can be introduced to the alkaline sugar solution, precipitating the lime as calcium carbonate (chalk) .
  • the chalk particles entrap som e impurities and adsorb others.
  • a recycling process builds up the size of chalk particles and a natural flocculation occurs where the heavy particles settle out in tanks.
  • Further addition of carbon dioxide precipitates more calcium from solution, which can be filtered off, leaving a cleaner sugar solution called "thin juice".
  • the thin juice can be concentrated via m ultiple-effect evaporation to m ake a "thick juice" , having sucrose content roughly of 65 % to
  • the thick juice can be fed to crystallisers and concentrated further by boiling under vacuum in large vessels and seeded with fine sugar crystals.
  • the resulting sugar crystal and syrup m ix is called a "massecuite".
  • the massecuite is passed to a centrifuge where the "mother liquor” is removed from the sugar crystals ("A" crystallisation) .
  • Rem aining syrup (“high green”) can be rinsed off with water and the crystals dried in a granulator. The remaining syrup can be fed to another crystalliser from which a second batch of sugar is produced (“B" crystallisation) . The syrup from the second (“low green”) crystalliser can be sent to a third crystalliser. There from a third batch of sugar is produced (“C” crystallisation) and syrup separated is typically molasses. All the main soluble im purities of thick juice are enriched to molasses. "Molasses” is defined according to Sugar Technology Beet and Cane Sugar Manufacture (Bartens, Berlin 1998, p.
  • the present invention provides an industrially useful process for the recovery of a brown food-grade sugar product from a sugar beet solution.
  • the process com prises i) providing a sugar beet solution, which contains m alodorous volatiles as a result of one or more purification processes, ii) subjecting said sugar beet solution to electrodialysis to provide an electrodialyzed liquid, wherefrom m alodorous volatiles are at least partly removed, and iii) recovering from said electrodialyzed liquid a product selected from liquid and solid brown sugar products of food-grade and com binations thereof.
  • said electrodialysis can be followed by a treatment with carbon or adsorbent resin to further remove off-flavours from said electrodialyzed liquid.
  • Activated carbon can be either granular or powder qualities. If only polishing is desired following qualities can be chosen : Jacobi Aquasorb ® (Jacobi Carbons Ltd) , Norit® Rox 0,8 or Norit® Darco (Norit N. V) . If also color removal is a target e.g. Chem iviron CPG (Chemviron Carbon Ltd.) quality can be used.
  • adsorbent resin Optipore® manufactured by Dow Chem icals
  • Carbon or adsorbent treatment can be carried out e.g. in temperatures up to 80 0 C and in concentrations up to 80 % and preferably at pH below pH 9.
  • the purification process com prises treatm ent of sugar beet juice under alkaline conditions such as the above-m entioned carbonation.
  • the sugar beet solution can be derived from the sugar beet juice by one or more processes selected from dilution, evaporation, crystallisation and combinations thereof and the sugar beet solution can comprise thick juice, thin juice, m assecuite, mother liquor, high greens, low greens, molasses and com binations thereof.
  • the resulting sugar beet solution may contain varying amounts of pyrazines depending on the used raw materials and purification conditions.
  • the sugar beet solution is subjected to electrodialysis, which is operated for removing at least 20% , preferably 30% or more of the total volatiles initially contained in said solution.
  • electrodialysis is operated for removing pyrazines initially contained in said sugar beet solution.
  • said electrodialysis is effective in removing 50% or more, preferably between 60 and 90 % of the pyrazines initially contained in said sugar beet solution.
  • the sugar beet solution contains m ethyl pyrazine and 2,5-m ethyl pyrazine and more than 80% , preferably 90% or more of said methyl pyrazine is removed and more than 50% , preferably 70% or more of the 2,5-dimethyl pyrazine is removed.
  • the electrodialysis com prises feeding said sugar beet solution at the dry solids concentration 1 0% to 50% , preferably 25% to 35% through anion and cation exchange m embranes, which operate above 40 0 C, preferably between 55 to 65 0 C.
  • suitable anion exchange membranes comprise organic fouling resistant and tem perature resistant Neosepta® AXE01 (Tokuyam a Corp. / Eurodia) and exam ples of suitable cation exchange m embranes com prise Neosepta® CMX (Tokuyama Corp. /Eurodia) .
  • an em bodim ent the sugar beet solution is subjected to electrodialysis at a pH between 6 and 9, preferably between 6.7 and 8, and the pH of said liquid after electrodialysis is between pH 4 and 6, preferably between 4.5 and 5.
  • the electrodialysis can also be operated to remove salts from said sugar beet solution.
  • I n a specific em bodim ent the electrodialysis is operated to remove at least 40% , preferably 60% or more of the inorganic and organic anions and cations and organic acids initially contained in said sugar beet solution.
  • the present invention provides an industrially useful process for the recovery of a brown food-grade sugar product from a sugar beet solution, wherein the product is selected from liquid and solid brown, food-grade sugar products and com binations thereof.
  • said recovery includes crystallisation and said solid food-grade sugar com prises brown sugar.
  • the crystallisation can be selected from evaporative boiling crystallisation and cooling crystallisation and com binations thereof.
  • the obtained brown sugar can be further refined by crystallisation to provide white sugar and "brown sugar molasses".
  • said recovery is concentration by evaporation and a liquid food-grade sugar product is selected from food-grade molasses, treacle and syrup.
  • an em bodim ent the sugar beet solution is beet molasses and it is subjected to electrodialysis, carbon or adsorbent resin treatm ent, and crystallisation, in that order, and a product selected from brown sugar and secondary electrodialyzed carbon-treated molasses is/are recovered after said crystallisation.
  • said sugar beet solution is beet molasses and it is subjected to electrodialysis, crystallisation and carbon or adsorbent resin treatm ent, in that order, and brown sugar is recovered after the crystallisation and carbon treated secondary electrodialyzed molasses is recovered after said carbon or adsorbent resin treatment.
  • the brown sugar and the secondary electrodialyzed molasses of various options are recovered essentially free of the off-flavours and the burnt solvent odours found in norm al brown sugar and molasses from sugar beet.
  • the obtained brown sugar can be further subjected to a treatm ent selected from drying, granulation, grinding, blending, coating and com binations thereof to provide a brown sugar product useful as a substitute for brown sugar products from sugar cane, and the obtained electrodialyzed molasses can be further subjected to a treatm ent selected from blending, inversion and com binations thereof to provide a molasses product useful as a substitute for molasses, treacle, syrup and soft brown sugar of sugar cane origin.
  • a solution of sugar beet molasses preferably from a conventional beet sugar process is subjected to electrodialysis (ED) to provide an electrodialyzed liquid, wherefrom m alodorous volatiles are at least partly removed.
  • the obtained electrodialyzed solution can be treated with carbon and the electrodialyzed carbon treated ( EDC) liquor is recovered as EDC-molasses.
  • EDC-molasses is a food-grade beet molasses that can be used as such as an ingredient, sweetener, flavourant and/or colourant in a nutritional, nutraceutical or pharmaceutical product.
  • the obtained electrodialyzed solution from beet molasses can be subjected to at least one crystallisation ( D-crystallisation) ( Fig. 2) .
  • the crystallisation separates the sugar from the organic and inorganic components in the sugar solution.
  • the sugar crystals are removed by centrifugation to provide crystallized sucrose ( ED- D-sugar) and secondary electrodialyzed molasses ( ED-D- Molasses) .
  • the crystallized sucrose ( ED- D-sugar) is recovered as brown sugar, which can be used as such as an ingredient, sweetener, flavourant and/or colourant in a nutritional, nutraceutical or pharmaceutical product. .
  • the brown sugar (ED- D-sugar, brown) can be refined by crystallisation to provide white sugar (ED- D-sugar, white) and "brown sugar molasses".
  • the secondary electrodialysed (ED- D) molasses is also recovered and it can be used for exam ple as treacle and/or for making acrylam ide-free soft brown sugar. Further purification of ED- D molasses can be effected by carbon treatm ent to obtain a carbon treated secondary electrodialyzed molasses ( ED-D-C) .
  • the obtained brown liquid or solid food-grade sugar product can be m ixed with other ingredient(s) and processed into an edible product selected from a dessert, ice-cream , confectionery, bakery, beverage and table sugar.
  • the invention provides use of electrodialysis for removing malodorous volatile com ponents from a sugar beet solution, which contains malodorous volatiles as a result of one or more purification processes.
  • a specific em bodim ent said electrodialysis is used for removing pyrazines from said solution.
  • electrodialysis is used for sugar beet solutions containing methyl pyrazine and 2,5-methyl pyrazine, and by the use of electrodialysis more than 80 % , preferably 90 % or more of said m ethyl pyrazine is removed and more than 50 % , preferably 70% or more of the 2,5-dim ethyl pyrazine is removed.
  • electrodialysis is com bined with a carbon or adsorbent resin treatm ent for removing off-flavours.
  • electrodialysis is for providing a beet-derived brown sugar and/or molasses suitable for substituting the corresponding product derived from cane sugar.
  • the invention provides a food-grade sugar beet product derived from a sugar beet solution, which contains m alodorous volatiles as a result of one or more purification processes, said product comprising a brown sugar or molasses product, which contains less than 0.5 ppm , preferably less than 0.15 ppm , volatile pyrazines and is essentially free of saponins or at least less than 50 mg/kg of molasses.
  • said product is essentially free of m ethyl pyrazine.
  • an em bodim ent the food-grade sugar beet product is derived from a sugar beet solution wherefrom the pyrazines contained therein have been removed by electrodialysis.
  • the product contains no more than 50 % , preferably no more than 30 % of the 2,5-dim ethyl pyrazine initially contained in said solution.
  • electrodialyzed molasses produced according to the invention is finally concentrated to the range from 68% to 80% dry solids (DS) to provide food- grade beet molasses, treacle or syrup, .
  • I t which contains sucrose 55 to 75% on DS, conductivity ash below 7 % on DS, preferably below 4 % on DS, and pyrazines less than 0.5 ppm m easured by Dynam ic headspace m ethod TCT.GC- MS (Kaipainen A. J of High Res. Chrom atogr. 1992, p 751 -755) , preferably less than 0.1 5 ppm .
  • Final product has dark or sem i dark colour and pleasant flavour.
  • the product according to the invention is preferably a beet derived product selected from brown sugar, electrodialyzed molasses, treacle, syrup and com binations thereof having colour, taste, odour and arom a acceptable to be used in food industry analogous to various corresponding cane sugar based brown sugar and molasses grades.
  • I n an em bodim ent the brown sugar product according to the invention is selected from soft brown sugar, coated brown sugar and free-flowing brown sugar.
  • I n a specific embodim ent said brown sugar has a colour ranging from 3000 to 1 1000 I CUMSA units and brown sugar product contains less than 0.01 ppm volatile pyrazines.
  • the invention also concerns an edible product, which is a nutritional, nutraceutical or pharm aceutical product comprising a brown sugar and/or molasses product according to the invention as ingredient, sweetener, flavourant and/or colourant.
  • an em bodim ent the edible product comprises a blend of said brown sugar and/or molasses with cane sugar derived sugar and/or molasses.
  • Exam ples of edible products comprise desserts, ice-cream , confectionery, bakery and beverages.
  • the food-grade sugar beet products according to the invention can be used as an ingredient, sweetener, flavourant and/or colourant in a nutritional, nutraceutical or pharmaceutical product.
  • the invention is illustrated further in the following Examples. It should be understood that this is done solely by way of exam ple and is not intended neither to delineate the scope of the invention nor lim it the ambit of the appended claims.
  • Example 1 com prises the following steps:
  • Pol The apparent sucrose content expressed as a percentage by m ass and determ ined by polarisation m ethod.
  • Pol Purity The percentage ratio of pol to the total soluble solids in a sugar product.
  • the feed molasses was first diluted from 79.0% refractom eter dry substance (RDS) to about 30% RDS before being fed to the Electrodializer Pilot Plant, EUR
  • ED increased the molasses sucrose purity by almost 1 1 units and significantly reduced the salty, sour, bitter, and beet tastes in the molasses. I t also elim inated the unpleasant burnt solvent odour.
  • the ED-molasses was thereafter subjected to carbon treatment.
  • the ED molasses was fed into an AquaFlowTM AF700 modular filter unit filled with Jacobis Aquasorb® H200 carbon.
  • the filter was supplied pre-filled with 300 kg of carbon.
  • the process was operated at 70 0 C at a flow rate of 1 50 litres per hour.
  • Carbon treatm ent further reduced beet taste and all off-odour exposing som e pleasant chocolate-like notes.
  • the EDC- D-sugar had both a pleasant m ild sweet taste and a pleasing visual red- brown appearance.
  • the ED treatm ent significantly reduced the sour taste of the molasses, while both
  • Example 2 com prises the following steps as shown in Fig 2:
  • the feed molasses was diluted from 77.8% refractom eter dry substance ( RDS) to about 30% RDS before being fed to the Electrodializer Pilot Plant, EUR 20 B 200- 1 0 using Neosepta® AXE01 and CMX exchange m em branes.
  • a 60% reduction in conductivity from 20 to 8 mS/cm was achieved at an operating tem perature of 55 0 C using a current density of 7 mA/cm2 and 1 V/cell.
  • the ED product molasses was subjected to a single evaporative crystallisation at 80 0 C in a 30 m 3 stirred vacuum pan with centre down-take. The sam e procedure as for final product crystallisation was used.
  • the massecuite was discharged into a strike receiver tank and cooled naturally under stirring to 50 0 C over a period of 48 hours. Thereafter the m assecuite was centrifuged in a continuous machine. The sugar crystals were separated, dissolved and recycled to the white sugar boiling pans. ED- D-molasses was separated from the sugar crystals and collected.
  • the results show the ED- D-molasses to have a about 2 % -units lower sucrose content (58.6% ) compared to the original untreated molasses (60.8% ) .
  • the ED- D-molasses was first conditioned by diluting to 58% to 60% RDS and heating to 60 0 C before being fed into a colum n filled with one litre of Chemviron CPG carbon at a flow rate of 500 m L/h. 13 litres of ED- D-molasses were treated over a period of 26 hours.
  • the results of the analyses made before ( ED- D- molasses) and after the carbon treatm ent ( ED- D-C-molasses) were as follows:
  • the carbon treatment removed a little colour and slightly increased the purity of the ED- D-C-molasses, but had m inor effect on the ash and pH levels.
  • the carbon treatm ent produced an ED- D-C-molasses free of off-flavours norm ally associated with normal beet molasses.
  • Example 3 comprised blending the carbon treated EDC- D-molasses, produced as explained in exam ple 1 , to food-grade cane molasses.
  • ED and carbon treated beet molasses lacks some of the significant liquorice and salm iac taste of cane molasses needed to spice up liquorice-type dark candies.
  • the ED and carbon treated beet molasses was blended to food-grade cane molasses at levels of up to 30% . Sensory tests of the blends were made by a panel of 28 participants. The judgem ent was EDC-molasses could be blended in the amount of 20-30% with food-grade cane without losing the desired liquorice and salm iac tastes necessary for m aking liquorice.
  • Example 4 com prised m aking ice cream with EDC-molasses according to Example 1 as an ingredient as follows:
  • the ice cream was judged to have a good, full caram el taste plus a slight liquorice taste. I t could easily have tolerated a higher dosage of EDC-molasses.
  • Example 5 com prised m aking toffee with EDC-molasses according to Exam ple 1 as an ingredient as follows:
  • the ingredients were stirred in a m icrowave safe bowl and put in the m icrowave oven at full effect (750W) for about 80-9Os.
  • 750W full effect
  • the m ixture was poured on a greased baking tray paper and cooled down before being cut into pieces.
  • the toffee had a good taste with pleasant chocolate/ cocoa after notes.
  • Example 6 com prised m aking bakery molasses as follows: 1 ) The concentration of EDC-molasses (according Example 1 ) was adjusted to 65% RDS;
  • Example 7 com prised making dark soft brown sugar by blending 9kg of EDC- D- sugar (according to Example 1 ) with 1 kg of EDC-molasses.
  • the product had a pleasing reddish brown colour and a distinctive sweet m ild taste.
  • Soft liquorice is normally m ade from food molasses of cane origin.
  • I n Exam ple 8 soft liquorice is made from the ED- D-C-molasses product of beet origin as produced in exam ple 2 as follows:
  • the taste profile of the test sample of 1 00 % replacem ent was slightly different. No odd flavour, but the taste profile was poorer and more narrow and m ilder than that of cane molasses.

Abstract

The invention relates to a process for the recovery of a brown food-grade sugar product from sugar beet solutions, which can be obtained from various beet sugar process streams, such as thin juice, thick ju ice and molasses. The process com prises providing a sugar beet solution, which contains malodorous volatiles as a result of one or more purif ication processes; subjecting said sugar beet solution to electrodialysis to provide an electrodialyzed liquid, wherefrom malodorous volatiles are at least partly removed; and recovering from said electrodialyzed liquid a product selected from liquid and solid brown sugar products of food-grade and combinations thereof. The invention also relates to food-grade beet sugar products derived from a sugar beet solution. These products are suitable for substituting the corresponding cane sugar derived products. In a further aspect the invention relates to the use of electrodialysis for removing malodorous volatile components from a sugar beet solution.

Description

A PROCESS FOR TH E RECOVERY OF A BROW N FOOD-GRAD E SUGAR PRODUCT FROM A SUGAR BEET SOLUTI ON
FI ELD OF THE I NVENTI ON
The present invention relates to the field of sugar m anufacturing industry and flavouring industry. More particularly, the invention relates to a process for the recovery of a brown food-grade sugar product from sugar beet solutions, which can be obtained from various beet sugar process streams, such as thin juice, thick juice and molasses. The invention also relates to novel food-grade beet sugar products derived from a sugar beet solution. The products of the invention are suitable for substituting the corresponding cane sugar derived products. The products according to the invention can be selected from brown sugar, electrodialyzed molasses, treacle, syrup and combinations thereof. Especially the invention relates to the production of food-grade beet molasses. The invention also relates to edible products com prising said novel food-grade beet sugar products. I n a further aspect the invention relates to the use of electrodialysis for removing m alodorous volatile components from a sugar beet solution.
BACKGROUND OF THE I NVENTI ON
Molasses is the final syrup residue remaining after crystallisation of sugar from either cane or beet juices. Only the syrup left from the final crystallisation stage is called molasses; intermediate syrups are referred to as high green and low green and these are recycled within the crystallisation process to m axim ise extraction. Molasses is one of the most valuable by-products of the sugar m anufacturing process. Both beet and cane molasses are widely used in the fermentation industries and in animal feed but only cane molasses as a food ingredient.
Molasses that com es from the sugar beet is different from cane molasses. Beet molasses contains over 50% sugar by dry weight, predom inantly sucrose but also containing sm all amounts of glucose and fructose. The non-sugar content includes e.g. am ino acids, organic acids, and m any salts such as calcium , potassium , oxalate and chloride. These are either as a result of concentration from the original plant material or as a result of chem icals used in the processing. As such, beet molasses is generally known to be very unpalatable and is m ainly used as an additive to animal feed or as a fermentation feedstock. Therefore, as an ingredient of food grade speciality brown sugars and molasses blends, only syrups of cane origin are used (Sugar Technology Beet and Cane Sugar Manufacture, P. W. van der Poel, H Schiweck, T. Schwartz, 1998, p 967 section 19.6) . Known substitutes in bakery product for syrups of cane origin are corn syrup, pure m aple syrup or even honey. However, these are more expensive than cane molasses. One of the aspects of this invention is the production of palatable syrup of beet origin suitable as an ingredient in brown sugars and brown syrups. This is done with the aid of electrodialysis.
I t is well known that pyrazines found in beet molasses do not exist in cane molasses and are one of the compounds distinguishing these two products. Pyrazines are form ed in alkaline conditions in the presence of glucose and am ino acids, which have great chem ical reactivity with respect to carbonyl com pounds, through the Maillard reaction. Beet juices contain m uch higher levels of am ino acids than cane juice (Sugar Technology Beet and Cane Sugar Manufacture, P.W. van der Poel, H Schiweck, T. Schwartz, 1998, p 143 and 156) in which m any of the am ino acids are only present in trace amounts. The higher levels of am ino acids in beet juices and the higher operating pH in the conventional beet sugar process are two factors which can explain the presence of pyrazines in sugar beet juices like thin juice, thick juice and molasses.
Pyrazines are known to be powerful arom a com pounds with odours ranging from nutty, roasted, m usty, to burnt solvent. I dentification and quantification by Marsili et al (Journal of Chromatographic Science, 1994, 32, 165- 171 ) of com pounds responsible for the off-odour of beet sugar identified 2,5-dim ethyl pyrazine as one of the com pounds likely to contribute to the characteristic off-odour of beet sugar. Marsili found also geosm in, acetic, butyric and isovaleric acids to produce odour characteristics of beet. Carbon treatm ent reduced acetic acid and also acetol levels. Acetol has a good odour, but is pungent in larger quantities.
Electrodialysis ( ED) as a technique is known from the 1950's and it is widely used for exam ple in desalting of water and whey and within the inorganic chem ical industry e.g. for recovering organic acids from solutions. Desalting of sugar cane or sugar beet solutions via ED has been established in 1960's to 80's in various patent publications. Electrodialysis separates salts from a sugar solution using alternate cation and anion exchange m em branes. This is done by passing a direct current through a m embrane stack, causing the anions to move through the anion exchange mem brane and the cations through the cation exchange m embrane. The cations cannot move through the anion exchange m em brane. US 3 799 806 discloses a process for the purification and clarification of sugar juices, involving ultrafiltration followed by purification with electrodialysis. Sugar is separated by crystallisation from the purified juice.
US 3 781 174 discloses a continuous process for producing refined sugar from juice extracted from sugarcane. This process comprises further removing the impurities and colouring m atter by using a com bination of ion-exchange resin and ion-exchange m embrane electrodialysis, concentrating the purified juice and crystallizing the concentrated juice to form refined sugar.
US 4 331 483 discloses a process for purifying beet juice by contacting the juice to be purified with at least two ion exchangers formed of a porous m ineral support covered with a film of cross-linked polymer containing or bearing quaternary am monium salt groups for at least one of the ion exchangers and sulfone groups for at least one of the other ion exchangers. The ion exchange is used for removing proteins, am ino acids and betaine. Further, the purified juice m ight be dem ineralized by ion exchange or electrodialysis. Sugar is then separated by crystallisation from the purified juice.
US 4 083 732 discloses a m ethod of treating fresh sugar cane juice at about room temperature which includes removing non-sugar impurities , concentrating the resulting cold, water white juice by reverse osmosis to form a syrup which is evaporated to form direct white sugar and edible molasses. Also a m ethod of removing ions from the syrup by electrodialysis to produce cane based edible molasses having a very low ash and m aple flavour is disclosed.
WO2003/018848 describes a process for the preparation of white and brown sugar from raw diffuser beet juice. The juice is purified by m embrane filtration at 70 to 95 0C on a filter having a cut-off between 2,000 and 500,000 Dalton and evaporated under vacuum to a thick juice. After concentration to dry m atter content of 25% to 35% by weight the m embrane filtrated juice can optionally be dem ineralized by electrodialysis and then further evaporated to a thick juice. A conventional multi-step evaporative crystallisation of the thick juice gives crops of white and brown sugar crystals. The brown sugar obtained has valuable organoleptic properties and produced molasses has a better taste and aroma than conventional beet molasses. The removal of non-sugar im purities by cross-flow m embrane filtration of the raw juice instead of carbonation leaves another pattern of created and rem ained impurities. Thus some impurities, which were removed by the conventional carbonation process, will remain in the juice and the others like pyrazines are not formed at all in this process.
Thus, electrodialysis is known as a method for desalinating sugar cane syrup or molasses of a relatively high concentration. I n case of sugar syrup or molasses, however, it has been considered defective in that organic non-sugar contents would adhere to and precipitate on the anion exchange film and make cleaning of films difficult. A m ethod for the reduction of fouling by the precipitation of calcium and silicon before electrodialysis is disclosed in US 4 492 601 . I t describes a process for clarifying and desalinating sugar cane syrup or molasses, wherein inorganic oxy-acid and organic acid im purities are removed from raw sugar cane or molasses solutions by the steps of ( 1 ) adm ixing with the raw sugar cane syrup or molasses solution a water-soluble chloride of an alkaline earth m etal ion which reacts with inorganic oxy-acid anions and radicals and with organic acids to form a water-insoluble precipitate of said oxy-acid anions and radicals and organic acids, (2) separating said precipitate from said solution, (3) diluting the precipitate-free solution, and (4) subjecting said diluted solution to an electrodialysis using cation exchange film and neutral film arranged in an alternating m anner.
The article "New technologies in the sugar industry" by Matild Eszterle (Cukoripar Mv vol 54, (2001 ) No 1 , pp 4- 1 0) discloses separation techniques used in sugar industry including chromatography and electrodialysis. These techniques are disclosed as alternatives for the purification of sugar juices. This article does not disclose any specific com bination of these techniques and it is only directed to provide a m ethod which would decrease the number of energy consum ing crystallisation steps.
ED has not com monly been used until late 1990's in sugar industry due to its high capital costs and due to fouling problems caused by anion products removed by ED from molasses. Various extensive pre-treatment methods to overcom e the fouling problem have been patented, e.g. US 4 71 1 722 and JP 58-082124.
The developm ent of fouling resistant and high temperature resistant anion exchange m embranes and the design of electrodialysis stacks has facilitated the econom ical use of ED in the sugar industry. Eurodia I ndustrie S. A. has established com m ercially viable ED technology for desalting of cane molasses, sugar beet syrup and liquid sugar. Lutin describes electrodialysis as a purification technology in the sugar industry especially to partially replace ion exchange resins for the dem ineralization and purification of sugar syrups (Zuckerindustrie 125, No 12, pp. 982-984, 2000 by Lutin) . I t should be noted that ion exchange technology does not provide an identical result to ED and that the regeneration of ion exchange resins necessarily involves the use of strong acids and bases while the ED resins are easily cleaned occasionally by an acid wash followed by an alkali wash with less chem icals than in ion exchange.
Further, alkali m etal cations have been suspected of being highly melassigenic by holding sugar in the molasses and preventing it from being recovered as crystalline sugar. Elm idaoui et al. (Elsevier, Desalination 148, 2002, pp. 143- 148) describe the removal of melassigenic ions especially Na+ , K+ and Ca2+ for beet sugar syrups by electrodialysis using an anion-exchange membrane.
William J. Colonna et. al ( Proceedings of Conference on Sugar Processing Research, New Orleans, April 1996) have identified som e specific sugar odorants including pyrazines and suggested processes to remove odorants from beet sugar. I n their experiments beet sugar odorants were removed using solid phase adsorbents, including Optipore ( manufactured by Dow Chem ical Company) a styrene-divinylbenzene resin derivatized with various functional groups, and Empore extractions disk (m anufactured by the 3M Com pany) consisting of Teflon m em branes derivatized with functional groups that bind specific organic compounds.
However, none of the above-m entioned prior art discloses a process wherein electrodialysis is used for removing m alodorous volatile com ponents from a beet sugar solution, wherein said solution contains m alodorous volatiles as a result of one or more purification processes of sugar beet derived juices.
Despite the advances m ade in the art, there exists a continued need for the developm ent of novel processes for the separation and recovery of sucrose components from beet sugar origin. Especially, there is a need to provide a brown food-grade sugar product from a beet sugar solution suitable for substituting the corresponding cane sugar derived products. The emphasis on "natural" foods in recent years has caused increased production of the darker types of breads and sweet goods, which often feature the inclusion of brown sugars and molasses. Both brown sugars and molasses based on cane are used in a wide variety of bakery foods for their contribution to flavour and colour in breads, cakes and cookies. Many of the prior art approaches discussed hereinabove involve the use of electrodialysis especially for removal of salts and organic acids. However, in the prior art electrodialysis has not been used for removing m alodorous volatile com ponents that are a result of one or more earlier purification processes of a beet sugar solution. Especially, from the prior art it is not known to produce a food-grade molasses from sugar beet solution.
Thus, the objective problem to be solved is to provide brown food-grade sugar products having improved colour, taste, odour and/or arom a from a sugar beet solution.
BRI EF DESCRI PTI ON OF THE I NVENTI ON
An object of the present invention is thus to provide a process and a product so as to so as to alleviate the above disadvantages. The objects of the invention are achieved by a process, product and uses which are characterized by what is stated in the independent claims. The preferred embodim ents of the invention are disclosed in the dependent claims.
The invention is based on the surprising finding that electrodialysis ( ED) can be used for removing m alodorous volatile components from a sugar beet solution. Especially, it was surprising that the undesired off-flavours and odours com prising pyrazines can be removed by ED. I t was known from the prior art to use ED for removal of ionic com pounds, but man skilled in the art would not have thought that non-ionic com pounds such as pyrazines could be removed as well.
An objective of the invention is to provide a process of treating sugar beet juices and especially norm al beet molasses to allow com mercial food-grade brown sugar and molasses or blends thereof to be made suitable for use in both baking and confectionery. Now it has been found that electrodialysis removes undesired off- flavours and odours found in norm al beet molasses from conventional sugar beet process. I n this way a treated molasses can be produced suitable for direct production of food grade molasses absent of the off-odours normally associated with beet molasses. A further advantage of the process is that the ED treatm ent increases the molasses purity by removing salts, which allows extra sugar to be crystallised from the molasses. Crystallisation followed by centrifugation and drying of the recovered crystalline sugar allows production of brown sugar absent of the off-odours normally associated with brown sugar from sugar beet origin. BRI EF DESCRI PTI ON OF THE DRAWI NGS
I n the following the invention will be described in greater detail by m eans of preferred embodiments with reference to the attached drawings, in which
Figure 1 is a schematic flow sheet of the inventive process according to an em bodim ent.
Figure 2 is a schematic flow sheet of the inventive process according to another em bodim ent.
SUMMARY OF THE I NVENTI ON
"Sugar beet" (Beta vulgaris) , a m em ber of the Chenopodiaceae subfam ily and the Am aranthaceae fam ily, is a plant whose root contains a high concentration of sucrose. "Beet sugar" is sucrose obtained from sugar beet and respectively "beet molasses" is molasses obtained from sugar beet.
A typical beet sugar production process com prises several steps. After reception at the processing plant the beet roots are washed, m echanically sliced, and passed to a diffuser to extract their sugar content into a water solution. The liquid, a sugar beet solution, exiting the diffuser is called "raw juice".
The raw juice contains many impurities that m ust be removed before crystallisation. These purifications processes do not only purify raw juice but also alter the chem ical composition of the raw juice. As an example of the changes in the chem ical com position is the formation of malodorous volatiles in the sugar beet solution. Although some of the m alodorous volatiles probably enter the sugar factory with the beets, others such as organic acids and pyrazines are form ed during processing. For exam ple pyrazines (known malodorous compounds) are form ed by the reaction of glucose with am ino acids such as glutam ine and lysine in purification by carbonation process.
A typical purification process in a sugar factory is "carbonation" , wherein the juice is first m ixed with hot m ilk of lime (a suspension of calcium hydroxide in water) . This treatment precipitates in some extent a num ber of im purities, including multivalent anions such as sulfate, phosphate, citrate and oxalate, which precipitate as their calcium salts and large organic molecules such as proteins, saponins and pectins, which aggregate in the presence of m ultivalent cations. I n addition, the alkaline conditions convert the sim ple sugars, glucose and fructose, along with the am ino acid glutam ine, to chem ically stable carboxylic acids and induce Maillard reaction and creation of unfavourable com pounds like pyrazines. Left untreated, these sugars and am ines would eventually frustrate crystallisation of the sucrose.
As a second step of carbonation, carbon dioxide can be introduced to the alkaline sugar solution, precipitating the lime as calcium carbonate (chalk) . The chalk particles entrap som e impurities and adsorb others. A recycling process builds up the size of chalk particles and a natural flocculation occurs where the heavy particles settle out in tanks. Further addition of carbon dioxide precipitates more calcium from solution, which can be filtered off, leaving a cleaner sugar solution called "thin juice". The thin juice can be concentrated via m ultiple-effect evaporation to m ake a "thick juice" , having sucrose content roughly of 65 % to
75 % on dry weight.
The thick juice can be fed to crystallisers and concentrated further by boiling under vacuum in large vessels and seeded with fine sugar crystals. The resulting sugar crystal and syrup m ix is called a "massecuite". The massecuite is passed to a centrifuge where the "mother liquor" is removed from the sugar crystals ("A" crystallisation) .
Rem aining syrup ("high green") can be rinsed off with water and the crystals dried in a granulator. The remaining syrup can be fed to another crystalliser from which a second batch of sugar is produced ("B" crystallisation) . The syrup from the second ("low green") crystalliser can be sent to a third crystalliser. There from a third batch of sugar is produced ("C" crystallisation) and syrup separated is typically molasses. All the main soluble im purities of thick juice are enriched to molasses. "Molasses" is defined according to Sugar Technology Beet and Cane Sugar Manufacture (Bartens, Berlin 1998, p. 1088) as the sugar-bearing product of the sugar end whose purity has been reduced to the point that further crystallisation of sugar is not econom ically feasible without special treatment of the molasses. European Union has in its regulation defined that food-grade molasses must contain less than 70% of DS (dry solids) of sugars (saccharose or its degradation products and other sugars like raffinose) to qualify as a molasses within EU-regulations.
I n connection with the present invention molasses according any of the above definitions or according any other known definition are considered as molasses. Further, the above definitions terms "carbonation" , "raw juice", "thick juice", "thin juice", "massecuite" and "mother liquor" should be considered as examples of definition of these terms and in connection with the present invention these terms are considered to include any other known definition in the art. As an example the amount of 2-ethyl-5 methyl pyrazines in beet based thick juice and molasses of conventional beet sugar process according to liquid-liquid extraction m ethod used by Pihlsgard (J. Agric. Food chem . 2000, 48, 4844-4850) is 330 and 265 nanograms/g sugar (i.e. 0.330 ppm and 0.265 ppm ) respectively. Measured by Kaipainen's dynam ic headspace method (25th I nt. Symp. On Capill. Chrom atography, May 13-1 7.2002 Garda) sum of eight several pyrazines in refinery beet syrup has been 0.35 ppm (at pH 5.5) and in cane refinery molasses 0.001 ppm .
As a first aspect the present invention provides an industrially useful process for the recovery of a brown food-grade sugar product from a sugar beet solution. The process com prises i) providing a sugar beet solution, which contains m alodorous volatiles as a result of one or more purification processes, ii) subjecting said sugar beet solution to electrodialysis to provide an electrodialyzed liquid, wherefrom m alodorous volatiles are at least partly removed, and iii) recovering from said electrodialyzed liquid a product selected from liquid and solid brown sugar products of food-grade and com binations thereof.
Recovery of liquid and solid food-grade sugar products from electrodialyzed liquid can com prise concentration, crystallisation, drying, dilution or com binations thereof. Concentration can be effected by evaporation or m embrane filtration. Liquid products are preferably concentrated to dry solids over 70 % .
I n order to enhance the removal of off-flavours from the sugar beet solution, said electrodialysis can be followed by a treatment with carbon or adsorbent resin to further remove off-flavours from said electrodialyzed liquid. Activated carbon can be either granular or powder qualities. If only polishing is desired following qualities can be chosen : Jacobi Aquasorb ® (Jacobi Carbons Ltd) , Norit® Rox 0,8 or Norit® Darco (Norit N. V) . If also color removal is a target e.g. Chem iviron CPG (Chemviron Carbon Ltd.) quality can be used. As an exam ple of suitable adsorbent resin Optipore® (manufactured by Dow Chem icals) can be m entioned. Carbon or adsorbent treatment can be carried out e.g. in temperatures up to 80 0C and in concentrations up to 80 % and preferably at pH below pH 9.
I n an embodiment of the invention the purification process com prises treatm ent of sugar beet juice under alkaline conditions such as the above-m entioned carbonation. The sugar beet solution can be derived from the sugar beet juice by one or more processes selected from dilution, evaporation, crystallisation and combinations thereof and the sugar beet solution can comprise thick juice, thin juice, m assecuite, mother liquor, high greens, low greens, molasses and com binations thereof. The resulting sugar beet solution may contain varying amounts of pyrazines depending on the used raw materials and purification conditions.
I n an embodim ent of the process the sugar beet solution is subjected to electrodialysis, which is operated for removing at least 20% , preferably 30% or more of the total volatiles initially contained in said solution. Especially said electrodialysis is operated for removing pyrazines initially contained in said sugar beet solution.
I n another embodiment said electrodialysis is effective in removing 50% or more, preferably between 60 and 90 % of the pyrazines initially contained in said sugar beet solution. I n a specific embodiment the sugar beet solution contains m ethyl pyrazine and 2,5-m ethyl pyrazine and more than 80% , preferably 90% or more of said methyl pyrazine is removed and more than 50% , preferably 70% or more of the 2,5-dimethyl pyrazine is removed.
I n an em bodim ent of the invention the electrodialysis com prises feeding said sugar beet solution at the dry solids concentration 1 0% to 50% , preferably 25% to 35% through anion and cation exchange m embranes, which operate above 40 0C, preferably between 55 to 65 0C. Examples of suitable anion exchange membranes comprise organic fouling resistant and tem perature resistant Neosepta® AXE01 (Tokuyam a Corp. / Eurodia) and exam ples of suitable cation exchange m embranes com prise Neosepta® CMX (Tokuyama Corp. /Eurodia) . I n an em bodim ent the sugar beet solution is subjected to electrodialysis at a pH between 6 and 9, preferably between 6.7 and 8, and the pH of said liquid after electrodialysis is between pH 4 and 6, preferably between 4.5 and 5.
I n accordance with the present invention the electrodialysis can also be operated to remove salts from said sugar beet solution. I n a specific em bodim ent the electrodialysis is operated to remove at least 40% , preferably 60% or more of the inorganic and organic anions and cations and organic acids initially contained in said sugar beet solution.
As m entioned the present invention provides an industrially useful process for the recovery of a brown food-grade sugar product from a sugar beet solution, wherein the product is selected from liquid and solid brown, food-grade sugar products and com binations thereof. I n an em bodiment said recovery includes crystallisation and said solid food-grade sugar com prises brown sugar. The crystallisation can be selected from evaporative boiling crystallisation and cooling crystallisation and com binations thereof. The obtained brown sugar can be further refined by crystallisation to provide white sugar and "brown sugar molasses".
I n another embodiment said recovery is concentration by evaporation and a liquid food-grade sugar product is selected from food-grade molasses, treacle and syrup.
I n an em bodim ent the sugar beet solution is beet molasses and it is subjected to electrodialysis, carbon or adsorbent resin treatm ent, and crystallisation, in that order, and a product selected from brown sugar and secondary electrodialyzed carbon-treated molasses is/are recovered after said crystallisation.
I n another embodiment said sugar beet solution is beet molasses and it is subjected to electrodialysis, crystallisation and carbon or adsorbent resin treatm ent, in that order, and brown sugar is recovered after the crystallisation and carbon treated secondary electrodialyzed molasses is recovered after said carbon or adsorbent resin treatment.
Preferably the brown sugar and the secondary electrodialyzed molasses of various options are recovered essentially free of the off-flavours and the burnt solvent odours found in norm al brown sugar and molasses from sugar beet.
The obtained brown sugar can be further subjected to a treatm ent selected from drying, granulation, grinding, blending, coating and com binations thereof to provide a brown sugar product useful as a substitute for brown sugar products from sugar cane, and the obtained electrodialyzed molasses can be further subjected to a treatm ent selected from blending, inversion and com binations thereof to provide a molasses product useful as a substitute for molasses, treacle, syrup and soft brown sugar of sugar cane origin.
I n an em bodim ent of the invention as illustrated in Figure 1 , a solution of sugar beet molasses preferably from a conventional beet sugar process is subjected to electrodialysis ( ED) to provide an electrodialyzed liquid, wherefrom m alodorous volatiles are at least partly removed. The obtained electrodialyzed solution can be treated with carbon and the electrodialyzed carbon treated ( EDC) liquor is recovered as EDC-molasses. This EDC-molasses is a food-grade beet molasses that can be used as such as an ingredient, sweetener, flavourant and/or colourant in a nutritional, nutraceutical or pharmaceutical product. On the other hand the obtained electrodialyzed solution from beet molasses can be subjected to at least one crystallisation ( D-crystallisation) ( Fig. 2) . The crystallisation separates the sugar from the organic and inorganic components in the sugar solution. The sugar crystals are removed by centrifugation to provide crystallized sucrose ( ED- D-sugar) and secondary electrodialyzed molasses ( ED-D- Molasses) . The crystallized sucrose ( ED- D-sugar) is recovered as brown sugar, which can be used as such as an ingredient, sweetener, flavourant and/or colourant in a nutritional, nutraceutical or pharmaceutical product. . The brown sugar ( ED- D-sugar, brown) can be refined by crystallisation to provide white sugar ( ED- D-sugar, white) and "brown sugar molasses". The secondary electrodialysed ( ED- D) molasses is also recovered and it can be used for exam ple as treacle and/or for making acrylam ide-free soft brown sugar. Further purification of ED- D molasses can be effected by carbon treatm ent to obtain a carbon treated secondary electrodialyzed molasses ( ED-D-C) .
The obtained brown liquid or solid food-grade sugar product can be m ixed with other ingredient(s) and processed into an edible product selected from a dessert, ice-cream , confectionery, bakery, beverage and table sugar.
As a second aspect the invention provides use of electrodialysis for removing malodorous volatile com ponents from a sugar beet solution, which contains malodorous volatiles as a result of one or more purification processes. I n a specific em bodim ent said electrodialysis is used for removing pyrazines from said solution. Especially electrodialysis is used for sugar beet solutions containing methyl pyrazine and 2,5-methyl pyrazine, and by the use of electrodialysis more than 80 % , preferably 90 % or more of said m ethyl pyrazine is removed and more than 50 % , preferably 70% or more of the 2,5-dim ethyl pyrazine is removed.
I n an embodiment the use of electrodialysis is com bined with a carbon or adsorbent resin treatm ent for removing off-flavours. Especially the use of electrodialysis is for providing a beet-derived brown sugar and/or molasses suitable for substituting the corresponding product derived from cane sugar.
As a third aspect the invention provides a food-grade sugar beet product derived from a sugar beet solution, which contains m alodorous volatiles as a result of one or more purification processes, said product comprising a brown sugar or molasses product, which contains less than 0.5 ppm , preferably less than 0.15 ppm , volatile pyrazines and is essentially free of saponins or at least less than 50 mg/kg of molasses. Preferably said product is essentially free of m ethyl pyrazine.
I n an em bodim ent the food-grade sugar beet product is derived from a sugar beet solution wherefrom the pyrazines contained therein have been removed by electrodialysis. Preferably the product contains no more than 50 % , preferably no more than 30 % of the 2,5-dim ethyl pyrazine initially contained in said solution.
I n another em bodim ent the food-grade sugar beet product is derived from beet molasses which has been purified by electrodialysis and carbon treatment.
Typically electrodialyzed molasses produced according to the invention is finally concentrated to the range from 68% to 80% dry solids (DS) to provide food- grade beet molasses, treacle or syrup, . I t which contains sucrose 55 to 75% on DS, conductivity ash below 7 % on DS, preferably below 4 % on DS, and pyrazines less than 0.5 ppm m easured by Dynam ic headspace m ethod TCT.GC- MS (Kaipainen A. J of High Res. Chrom atogr. 1992, p 751 -755) , preferably less than 0.1 5 ppm . Final product has dark or sem i dark colour and pleasant flavour.
The product according to the invention is preferably a beet derived product selected from brown sugar, electrodialyzed molasses, treacle, syrup and com binations thereof having colour, taste, odour and arom a acceptable to be used in food industry analogous to various corresponding cane sugar based brown sugar and molasses grades. I n an em bodim ent the brown sugar product according to the invention is selected from soft brown sugar, coated brown sugar and free-flowing brown sugar. I n a specific embodim ent said brown sugar has a colour ranging from 3000 to 1 1000 I CUMSA units and brown sugar product contains less than 0.01 ppm volatile pyrazines.
The invention also concerns an edible product, which is a nutritional, nutraceutical or pharm aceutical product comprising a brown sugar and/or molasses product according to the invention as ingredient, sweetener, flavourant and/or colourant. I n an em bodim ent the edible product comprises a blend of said brown sugar and/or molasses with cane sugar derived sugar and/or molasses. Exam ples of edible products comprise desserts, ice-cream , confectionery, bakery and beverages.
The food-grade sugar beet products according to the invention can be used as an ingredient, sweetener, flavourant and/or colourant in a nutritional, nutraceutical or pharmaceutical product. The invention is illustrated further in the following Examples. It should be understood that this is done solely by way of exam ple and is not intended neither to delineate the scope of the invention nor lim it the ambit of the appended claims.
EXAMPLES
Example 1
Example 1 com prises the following steps:
1 ) Electrodialysis ( ED) of normal sugar beet factory molasses producing a purified ED-molasses with reduced odour and off-taste; 2) Carbon treatment of purified ED-molasses producing treated EDC- molasses essentially free of off-odours and off-tastes, suitable for m aking molasses blends; 3) Evaporative crystallisation of the purified and carbon treated EDC- molasses producing an EDC-massecuite; 4) Centrifugation of the EDC-m assecuite producing a brown sugar and an
EDC- D-molasses exhausted of sugar and sim ilar in purity to norm al factory molasses.
The com position of the beet molasses fed to the ED unit was analysed as follows:
Figure imgf000016_0001
Pol = The apparent sucrose content expressed as a percentage by m ass and determ ined by polarisation m ethod.
Pol Purity = The percentage ratio of pol to the total soluble solids in a sugar product.
Electrodialysis:
The feed molasses was first diluted from 79.0% refractom eter dry substance (RDS) to about 30% RDS before being fed to the Electrodializer Pilot Plant, EUR
20 B 200- 10, constructed in co-operation with Eurodia I ndustrie SA using Neosepta® AXE01 and CMX exchange mem branes. A 70% reduction in conductivity was achieved at an operating temperature of 55 0C using a current density of 7 mA/cm2 and 1 V/ cell. Afterwards the ED molasses was pH adjusted to a neutral pH using sodium hydroxide and re-concentrated in a falling-film evaporator.
Analysis of the ED treated and evaporated molasses gave the following results:
Figure imgf000017_0001
ED increased the molasses sucrose purity by almost 1 1 units and significantly reduced the salty, sour, bitter, and beet tastes in the molasses. I t also elim inated the unpleasant burnt solvent odour. The ED-molasses was thereafter subjected to carbon treatment.
Carbon treatm ent :
The ED molasses was fed into an AquaFlow™ AF700 modular filter unit filled with Jacobis Aquasorb® H200 carbon. The filter was supplied pre-filled with 300 kg of carbon. The process was operated at 70 0C at a flow rate of 1 50 litres per hour.
Analysis of the resultant carbon treated EDC-molasses gave the following results:
Figure imgf000017_0002
Carbon treatm ent further reduced beet taste and all off-odour exposing som e pleasant chocolate-like notes.
Crystallisation : A 300 litre pilot DDS type evaporative batch crystalliser with stirrer was used. The carbon treated EDC-molasses was concentrated under vacuum at 80 0C and seeded with sugar crystals. These were grown by further concentration for about ten hours exhausting the EDC-molasses of crystallisable sucrose. The hot m assecuite was then centrifuged and the sugar crystals removed from the final exhausted molasses.
Analysis of this final molasses or EDC- D- molasses gave the following results:
Figure imgf000018_0001
The purity of the EDC- D-molasses could have been further reduced if the m assecuite had been cooled to 45 0C before centrifugation as norm ally done on a factory-scale to maxim ise crystal yield.
Analysis of the brown EDC- D-sugar gave the following results:
Figure imgf000018_0002
The EDC- D-sugar had both a pleasant m ild sweet taste and a pleasing visual red- brown appearance.
Aroma Profile Analysis:
Analysis of Volatile Organic Com pounds by Dynam ic Headspace TCT-GC-MS was done on beet molasses after ED-treatm ent ( ED) and after ED and carbon treatm ent ( ED-C) . A total of 27 volatile com pounds were identified and sem i- quantified in all three sam ples. Som e of the identified compounds were present in concentrations exceeding their odour threshold. The total amount of the volatiles is significantly reduced after ED and ED-carbon treatm ent (see table below) . Volatile Organic Compounds I dentified in molasses and treated by TCT-GC-MS (Analytical results for volatiles are mg/kg on as is bases) :
Figure imgf000019_0001
a) Tentative identification, by m ass spectrum library only, no model com pounds analysed. b) Approximate concentration level, calculated using I STD only, one digit valid only. c) Empty cell = not detected, detection lim it about 0.005 mg/kg. d) 2-Methyl- Propanal = I sobutyraldehyde; Mequinol = 2-Methoxy- Phenol From the above table the total amounts of pyrazines can be calculated in each case. The norm al beet molasses contains about 1 .02 mg/kg of pyrazines, whereas the ED treated molasses contains only about 0.1 5 mg/kg of pyrazines. The carbon treatm ent reduces even further the total amount pyrazines. The ED and carbon treated molasses contains about 0.13 mg/kg of pyrazines.
Sensory Analysis:
Sensory analysis by both sniffing and tasting was done to evaluate both odours and flavours of the beet molasses and brown sugar before and after ED and carbon treatment. The most significant im provem ent was removal of the pungent burnt solvent odour present in norm al untreated beet molasses. This enabled brown sugar to be produced from treated molasses absent of a pungent burnt solvent odour, which is otherwise not possible from normal beet molasses.
The ED treatm ent significantly reduced the sour taste of the molasses, while both
ED and carbon treatments removed bitter taste. The removal of the pungent burnt solvent odour and sour and bitter tastes allowed more pleasant caram el and surprising chocolate notes to become noticeable as well as a slight liquorice taste.
Sensory analyses indicated EDC-molasses as a suitable for molasses blends, icecream , toffee, soft brown sugar and for m aking granulated brown sugar.
Example 2
Example 2 com prises the following steps as shown in Fig 2:
1 ) Electrodialysis ( ED) of norm al untreated sugar beet factory molasses to produce a purified ED-molasses;
2) Evaporative crystallisation of the purified ED-molasses on factory-scale using a 30 m3 batch vacuum pan to produce an ED- D-m assecuite; 3) Cooling crystallisation of the ED- D-m assecuite from 80 0C to 50 0C over
48 hours by natural cooling in a stirred strike receiver;
4) Centrifugation of the ED- D-massecuite by a continuous centrifuge producing a brown sugar and an ED- D-molasses exhausted of sugar and of sim ilar purity to normal untreated factory molasses; 5) Refining of the brown sugar to white sugar in the traditional way by re- dissolving and re-crystallisation ; 6) Carbon treatm ent of the ED-D-molasses to produce and ED- D-C-molasses.
The process steps are illustrated in the block diagram in Figure 2. Electrodialysis:
The feed molasses was diluted from 77.8% refractom eter dry substance ( RDS) to about 30% RDS before being fed to the Electrodializer Pilot Plant, EUR 20 B 200- 1 0 using Neosepta® AXE01 and CMX exchange m em branes. A 60% reduction in conductivity from 20 to 8 mS/cm was achieved at an operating tem perature of 55 0C using a current density of 7 mA/cm2 and 1 V/cell.
Analysis of the molasses before and after ED gave the following results:
Figure imgf000021_0001
ED increased sucrose purity of molasses from 60.8 % up to 70.7 % on RDS. There was no colour removal. The pH of product molasses was im m ediately increased from 4.9 to 8.1 with sodium hydroxide to avoid sucrose inversion. The ED product molasses was evaporated in a falling-film evaporator from 28.1 % to 74.6% RDS.
Crystallisation :
The ED product molasses was subjected to a single evaporative crystallisation at 80 0C in a 30 m3 stirred vacuum pan with centre down-take. The sam e procedure as for final product crystallisation was used.
After evaporative crystallisation the massecuite was discharged into a strike receiver tank and cooled naturally under stirring to 50 0C over a period of 48 hours. Thereafter the m assecuite was centrifuged in a continuous machine. The sugar crystals were separated, dissolved and recycled to the white sugar boiling pans. ED- D-molasses was separated from the sugar crystals and collected.
Analysis gave the following results:
Figure imgf000021_0002
Figure imgf000022_0001
The results show the ED- D-molasses to have a about 2 % -units lower sucrose content (58.6% ) compared to the original untreated molasses (60.8% ) .
Analysis of the ED- D-sugar recovered by centrifugation gave the following results:
Figure imgf000022_0002
Carbon Treatment :
The ED- D-molasses was first conditioned by diluting to 58% to 60% RDS and heating to 60 0C before being fed into a colum n filled with one litre of Chemviron CPG carbon at a flow rate of 500 m L/h. 13 litres of ED- D-molasses were treated over a period of 26 hours. The results of the analyses made before ( ED- D- molasses) and after the carbon treatm ent ( ED- D-C-molasses) were as follows:
Figure imgf000022_0003
The carbon treatment removed a little colour and slightly increased the purity of the ED- D-C-molasses, but had m inor effect on the ash and pH levels. The carbon treatm ent produced an ED- D-C-molasses free of off-flavours norm ally associated with normal beet molasses.
Example 3
Example 3 comprised blending the carbon treated EDC- D-molasses, produced as explained in exam ple 1 , to food-grade cane molasses.
ED and carbon treated beet molasses lacks some of the significant liquorice and salm iac taste of cane molasses needed to spice up liquorice-type dark candies. To make a product suitable for m aking liquorice, the ED and carbon treated beet molasses was blended to food-grade cane molasses at levels of up to 30% . Sensory tests of the blends were made by a panel of 28 participants. The judgem ent was EDC-molasses could be blended in the amount of 20-30% with food-grade cane without losing the desired liquorice and salm iac tastes necessary for m aking liquorice.
Example 4
Example 4 com prised m aking ice cream with EDC-molasses according to Example 1 as an ingredient as follows:
Figure imgf000023_0001
I ce cream process: 1 . Mix liquid ingredients at 20-22 0C
2. Mix dry ingredients and add to water phase at 20-22 0C
3. Add flavouring and colouring 4. I ncrease tem perature to 70 0C during m ixing
5. Homogenise at : 78 °C/200 bar
6. Pasteurise at: 84 °C/30 sec on the plate heat exchanger
7. Cool to 5 0C 8. Ageing overnight in ice water
9. Freezing, drawing temperature 5.0 0C, light extrusion with 100% overrun
1 0. Fill
1 1 . Overnight freezing in hardening tunnel at -30 0C 12. Store at -25 0C
The ice cream was judged to have a good, full caram el taste plus a slight liquorice taste. I t could easily have tolerated a higher dosage of EDC-molasses.
Example 5
Example 5 com prised m aking toffee with EDC-molasses according to Exam ple 1 as an ingredient as follows:
1 dl cream
1 dl EDC-molasses
The ingredients were stirred in a m icrowave safe bowl and put in the m icrowave oven at full effect (750W) for about 80-9Os. When the toffee was ready the m ixture was poured on a greased baking tray paper and cooled down before being cut into pieces.
The toffee had a good taste with pleasant chocolate/ cocoa after notes.
Example 6
Example 6 com prised m aking bakery molasses as follows: 1 ) The concentration of EDC-molasses (according Example 1 ) was adjusted to 65% RDS;
2) The pH was adjusted to between 4.0 and 5.6 with 6% HCI;
3) 1 .3 kg of the EDC-molasses was heated to 60 0C;
4) 2 m l_ of enzyme solution (invertase from Baker's yeast) was added; 5) The m ixture was stored in a warm oven at 70 0C for 48hours to allow the sucrose to be inverted.
6) The enzym e activity was then stopped by heat treatm ent at 90 to 95 0C for 30 m inutes. 7) The desired invert level was achieved by blending the original and the inverted EDC-molasses in amounts giving a desired pol purity of - 25 units.
8) The pH was then adjusted to between 5.6 and 6.0 with 45% sodium hydroxide.
9) The concentration was adjusted to - 79% RDS by evaporation under vacuum .
The inversion process gave the EDC-molasses a sweeter and m ilder taste making it suitable as a Bakery Molasses.
Example 7
Example 7 com prised making dark soft brown sugar by blending 9kg of EDC- D- sugar (according to Example 1 ) with 1 kg of EDC-molasses.
The analysis of the resultant product was as follows:
Figure imgf000025_0001
The product had a pleasing reddish brown colour and a distinctive sweet m ild taste.
Example 8
Soft liquorice is normally m ade from food molasses of cane origin. I n Exam ple 8 soft liquorice is made from the ED- D-C-molasses product of beet origin as produced in exam ple 2 as follows:
Formulation:
%
A Wheat flour 21 .0
Water 23.9
Liquorice powder 2.4
B Partially inverted Sugar
Solution 41 .9
Food Molasses 10.5 Carbon Black 0.1 8 Salt 0.09
Aniseed oil 0.03
Process:
1 . Mix wheat flour, liquorice powder and water homogenous slurry.
2. Add into the cooker sugar solution, half of the food molasses and the slurry. Heat to boiling point and add the rest of the food molasses, carbon black and salt.
3. Cook until the dry substance (RDS) is 70 to 75 % .
4. Add aniseed oil after heating has been stopped and m ix for 5 m inutes.
5. Take liquorice m ass out.
6. Form during following day or when the tem perature is about 90 0C. 7. Dry the form ed liquorice in cabins at 40 to 50 0C. Water content in product is 1 7 to 20 % .
Trials:
Three different trials were done replacing in form ula 10 % , 30 % and 1 00 % of Cane Food Molasses with ED- D-C-molasses. Technically processing of all trials was sim ilar to the reference sam ple. The taste profile of 10 % and 30 % replacem ent was also as good as the reference. The strong liquorice taste masked slight differences noticed in pure Cane Food Molasses with 30% ED- D-C- molasses.
The taste profile of the test sample of 1 00 % replacem ent was slightly different. No odd flavour, but the taste profile was poorer and more narrow and m ilder than that of cane molasses.
Example 9 - Comparison results
Com parison analyses of molasses of present invention ( Example 1 ) and molasses from process using UF and ED for purification of sugar beet raw juice.
Analysis of volatile com pounds by Dynam ic Headspace TCT-GC-MS of (a) ED- treated beet molasses from the traditional juice purification process (carbonation) and (b) beet molasses produced according to the process described in WO2003/018848 by purifying raw juice with membrane filtration (UF) and ED- treatm ent are shown in the following table. The level of saponins was for molasses of the present invention 43 mg/kg of molasses and for UF-ED treated molasses 164 mg/kg of molasses..
Figure imgf000027_0001
Empty cell = not detected, detection limit about 0.005 mg/kg

Claims

CLAI MS
1 . An industrially useful process for the recovery of a brown food-grade sugar product from a sugar beet solution com prising
- providing a sugar beet solution, which contains m alodorous volatiles as a result of one or more purification processes;
- subjecting said sugar beet solution to electrodialysis to provide an electrodialyzed liquid, wherefrom malodorous volatiles are at least partly removed; and
- recovering from said electrodialyzed liquid a product selected from liquid and solid brown sugar products of food-grade and combinations thereof.
2. Process according to claim 1 , wherein in order to enhance the removal of off- flavours from said sugar beet solution, said electrodialysis is followed by a treatment with carbon or adsorbent resin to further remove off-flavours from said electrodialyzed liquid.
3. Process according to claim 1 , wherein said one or more purification processes com prises treatm ent of sugar beet raw juice under alkaline conditions.
4. Process according to any of the claims 1 to 3, wherein said purification process is a carbonation process.
5. Process according to claim 3 or 4, wherein said sugar beet solution is derived from said sugar beet juice by one or more processes selected from dilution, evaporation, crystallisation and combinations thereof.
6. Process according to claim 5, wherein said sugar beet solution comprises beet molasses.
7. Process according to any one of claims 1 to 6, wherein said electrodialysis is operated for removing at least 20% , preferably 30% or more of the total volatiles initially contained in said solution.
8. Process according to any one of claims 1 to 7, wherein said m alodorous volatiles com prise pyrazines.
9. Process according to any one of claims 1 to 8, wherein said electrodialysis is operated for removing pyrazines initially contained in said sugar beet solution.
1 0. Process according to claim 9, wherein said electrodialysis is effective in removing 50% or more, preferably between 60 and 90 % of the pyrazines initially contained in said sugar beet solution.
1 1 . Process according to claim 9, wherein said sugar beet solution contains m ethyl pyrazine and 2,5-m ethyl pyrazine and more than 80% , preferably 90% or more of said methyl pyrazine is removed and more than 50% , preferably 70% or more of the 2,5-dimethyl pyrazine is removed.
12. Process according to any one of claims 1 to 1 1 , wherein said recovery includes crystallisation and said solid food-grade sugar com prises brown sugar.
13. Process according to any one of claims 1 to 12, wherein said recovered liquid brown food-grade sugar product is selected from food-grade molasses, treacle and syrup.
14. Process according to claim 12, wherein said brown sugar is refined by crystallisation to provide white sugar and secondary electrodialyzed molasses.
1 5. Process according to any one of claims 1 to 14, wherein said electrodialysis com prises feeding said sugar beet solution through anion and cation exchange mem branes, which operate above 40 0C, preferably 55-65 0C.
1 6. Process according to claim 1 5, wherein said anion exchange mem brane com prises a fouling resistant and tem perature resistant Neosepta ® AXE01 .
1 7. Process according to claim 1 5, wherein said cation exchange m em brane com prises a Neosepta® CMX.
18. Process according to any one of claims 1 to 17, wherein the electrodialysis com prises feeding said sugar beet solution at the dry solids concentration 25% to 35% through anion and cation exchange mem branes.
19. Process according to any one of claims 1 to 18, wherein said sugar beet solution is subjected to electrodialysis at a pH between 6 and 9, preferably between 6.7 and 8.
20. Process according to claim 19, wherein the pH of said liquid after electrodialysis is between pH 4 and 6, preferably between 4.5 and 5.
21 . Process according to any one of claims 1 to 20, wherein said electrodialysis is operated to also remove salts from said sugar beet solution.
22. Process according to claim 21 , wherein said electrodialysis is operated to remove at least 40% , preferably 60% or more of the inorganic and organic anions and cations and organic acids initially contained in said sugar beet solution.
23. Process according to claim 12, wherein said crystallisation is selected from evaporative boiling crystallisation and cooling crystallisation and combinations thereof.
24. Process according to claim 12, wherein said sugar beet solution is beet molasses and it is subjected to electrodialysis, carbon or adsorbent resin treatment, and crystallisation, in that order, and a product selected from brown sugar and secondary electrodialyzed carbon-treated molasses is/are recovered after said crystallisation.
25. Process according to claim 12, wherein said sugar beet solution is beet molasses and it is subjected to electrodialysis, crystallisation and carbon or adsorbent resin treatm ent, in that order, and brown sugar is recovered after said crystallisation and carbon-treated secondary electrodialyzed molasses is recovered after said carbon or adsorbent resin treatment.
26. Process according to claim 24 or 25, wherein said brown sugar and said electrodialyzed carbon-treated molasses are recovered essentially free of the off-flavours and the burnt solvent odours found in norm al brown sugar and molasses from sugar beet.
27. Process according to claim 26, wherein said brown sugar is subjected to a treatm ent selected from drying, granulation, grinding, blending, coating and com binations thereof to provide a brown sugar product useful as a substitute for brown sugar products from sugar cane.
28. Process according to claim 26, wherein said electrodialyzed molasses is subjected to a treatm ent selected from blending, inversion and combinations thereof to provide a molasses product useful as a substitute for molasses, treacle, syrup and soft brown sugar of cane sugar origin.
29. Process according to claim 1 , wherein said liquid or solid brown sugar product of food-grade is m ixed with other ingredient(s) and processed into an edible product selected from a dessert, ice-cream , confectionery, bakery, beverage and table sugar.
30. Use of electrodialysis for removing m alodorous volatile com ponents from a sugar beet solution, which contains malodorous volatiles as a result of one or more purification processes.
31 . Use according to claim 30, wherein said electrodialysis is used for removing pyrazines from said solution.
32. Use according to claim 31 , wherein said sugar beet solution contains m ethyl pyrazine and 2,5-m ethyl pyrazine and more than 80 % , preferably 90 % or more of said m ethyl pyrazine is removed and more than 50 % , preferably 70% or more of the 2,5-dim ethyl pyrazine is removed.
33. Use according to claim 28, wherein said electrodialysis is combined with a carbon or adsorbent resin treatment for removing off-flavours.
34. Use according to any one of claims 28 to 30 for providing a beet-derived brown sugar and/or molasses suitable for substituting the corresponding product derived from cane sugar.
35. A food-grade sugar beet product derived from a sugar beet solution, which contains malodorous volatiles as a result of one or more purification processes, said product comprising a brown sugar or molasses product, which contains less than 0.5 ppm volatile pyrazines and is essentially free of saponins.
36. A food-grade sugar beet product according to claim 35, wherein said molasses product contains less than 0.1 5 ppm volatile pyrazines.
37. A food-grade sugar beet product according to claim 35, wherein said brown sugar product contains less than 0.01 ppm volatile pyrazines.
38. Product according to any one of claims 35 to 37, wherein pyrazines contained in said sugar beet solution have been removed by electrodialysis.
39. Product according to any one of claims 35 to 37, which is essentially free of m ethyl pyrazine.
40. Product according to claim 38, which contains no more than 50 % , preferably no more than 30 % of the 2,5-dim ethyl pyrazine initially contained in said solution.
41 . Product according to claim 35, which is derived from beet molasses and which has been purified by electrodialysis and carbon treatm ent.
42. Product according to claim 35, which is a brown sugar product selected from soft brown sugar, coated brown sugar and free-flowing brown sugar.
43. Product according to claim 42, wherein said brown sugar has a colour ranging from 3000 to 1 1 000 I CUMSA units.
44. Product according to claim 35, wherein said product is a beet derived product selected from brown sugar, electrodialyzed molasses, treacle, syrup and com binations thereof having colour, taste, odour and aroma acceptable to be used in food industry analogous to sugar cane based brown sugar and molasses grades.
45. Edible product, which is a nutritional, nutraceutical or pharm aceutical product com prising a brown sugar and/or molasses product according to claim 35 as ingredient, sweetener, flavourant and/or colourant.
46. Edible product according to claim 45, which comprises an edible product selected from desserts, ice-cream , confectionery, bakery and beverages.
47. Edible product according to claim 45, which comprises a blend of said brown sugar and/or molasses with cane sugar derived sugar and/or molasses.
48. Use of the product of claim 35 as an ingredient, sweetener, flavourant and/or colourant in a nutritional, nutraceutical or pharm aceutical product.
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